Organic sulfonates



United States Patent 3,458,447 ORGANIC SULFONATES Andrew Shultz, Williamsville, N.Y., assignor t0 Allied Chemical Corporation, New York, N.Y., a corporation of New York No Drawing. Filed Feb. 15, 1966, Ser. No. 527,526 Int. Cl. (311d 3/065; C07c 143/28 US. Cl. 252-137 18 Claims ABSTRACT OF THE DISCLOSURE Novel, low foaming, highly biodegradable alkyl aryl sufonates are provided by sulfonating that portion of an aryl alkylation product containing up to 50% by weight monoalkylbenzens, from 10% to 50% by weight dialkylindanes and dialkyltetrahydronaphthalenes and about 35% to 90% by weight of a mixture of diphenylalkanes and dialkylbenzenes.

Synthetic detergents have found wide use in industrial and household cleaning, particularly in the laundering of fabrics. A property desired in materials for such uses is high detergency. However, there are additional properties which are highly desirable in a detergent, such as low cost and high biodegradability. For a number of years, high foaming was also considered a desirable property in detergents. However, in the recent years it has been recognized that high foaming detergents have certain disadvantages. Consequently, a market for low foaming synthetic detergents has developed and there has been continuing effort to provide synthetic detergents which not only have commercially acceptable detergent properties and are low in cost and highly biodegradable, but are also low foaming.

One of the disadvantages of high foaming in a detergent is that the concentration in which high foaming detergents can be used is necessarily limited in order to avoid excessive foaming. In laundering fabrics excesive foaming is undesirable since additional rinse cycles are required to remove the detergent completely and restore the hand of the cloth. Excessive foaming is particularly undesirable in top-loading washing machines, since foam overflow occurs resulting in deposition of detergent particules into the shell of the washing machine casing corrosion and clogging thereof. In addition, soil particles remaining in suspension throughout the foam may be redeposited, during the rinse cycle, on the garments being washed. A high foam density furnishes a cushioning effect which reduces actual contact of the washing machine agitator with the garments being washed and of the garments with each other, thereby reducing the extent of physical loosening of dirt particles from the fibers.

Similarly, in front-loading machines, a high foam concentration inhibits efficient contact of the garments being washed with each other and with the sides of the washer, thereby reducing physical loosening of dirt particles from fiber interstices.

In other cleaning applications excessive foaming is similarly undesirable; disadvantageously requiring additional rinsing thus increasing operational times and water requirements.

The anionic alkylbenzene sulfonates having satisfactory detergent and biodegradability properties and relatively low cost are, however, high foaming. In order to overcome the high foaming of such detergents, it is necessary to add relatively expensive foam-depressing agents, thereby in creasing the cost of the product without improving its cleansing action.

Nonionic detergents, such as the ethylene oxide condensates, having satisfactory detergent and biodegradability properties and low foaming, are, however, relatively high in cost.

High biodegradability, i.e. rapid decomposition by micro-organisms, is desirable in detergents as detergents of low biodegradability stand accused of being a factor in the rising rate of pollution of resh water sources, which is increasingly becoming the subject of public and commercial concern.

Accordingly it is an object of this invention to provide compositions of low cost having high detergent properties.

It is a further object of this invention to provide low cost compositions which have high detergent properties and low foamnig and high biodegradability. Other objects and advantges will be apparent form the following detailed description.

I have discovered that these and other objects are achieved by the anionic surface active compositions of this invention, hereinafter referred to as the organic sulfonates of this invention, which are the sulfonates of a hydrocarbon mixture having (A) up to about 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkyl'benzenes consisting predominantly of 2-phenylalkanes, (B) from about 10% to 50% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and (C) from about 35% to 90% by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

Particularly useful organic sulfonates of this invention are the sulfonates of a hydrocarbon mixture having (A) from about 15% to 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of 2-phenylalkanes, (B) from about 10% to 40% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a miximum of 15 for each molecule, and (C) from about 35% to by Weight of a mixture of diphenylalkanes and dialkylbenzes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

Other particularly useful organic sulfonates of this invention are the sulfonates of a hydrocarbon mixture having (A) up to about 10% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of Z-phenylalkanes, (B) from about 10% to 50% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule and (C) from about 45% to by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

Other particularly useful organic sulfonates of this invention are the sulfonates of a hydrocarbon mixture having (A) from about 30% to 40% by Weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of Z-phenylalkanes, (B) from about to by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and (C) from about 45% to 60% by weight of a mixture of diphenylalkancs and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms. Such sulfonates combine excellent detersive and cleansing properties with a surprisingly high biodegradability of at least 90 percent, in spite of the complex nature of the components of the hydrocarbon mixture from which these sulfonates are derived.

The term organic sulfonates as used herein is intended to describe organic compounds having sulfonate groups which may be sulfonic acids or salts thereof, including alkali and alkaline earth metal, ammonium and organic amine salts.

The organic sulfonates of this invention are low in cost, i.e., comparable in cost to the conventional anionic detergents, as they can be produced from readily available low cost raw materials by a process, hereinafter described.

The organic sulfonates of this invention can be produced by a process of this invention comprising (A) passing chlorine in intimate contact with an essentially linear alkane hydrocarbon having 8 to 18 carbon atoms, or mixture thereof, in an amount insufiicient to chlorinate all the alkane and to produce primarily monochloroalkanes, (B) reacting the chlorination mixture produced by step (A) with a large excess of benzene in the presence of a Friedel-Crafts catalyst under alkylating conditions to produce an alkylation mixture, (C) recovering by fractional distillation of said alkylation mixture an alkylate fraction composed of (a) up to about 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of 2-phenylalkanes; (b) from about 10% to 50% by Weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule; and (c) from about 35% to 90% by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms; (D) sulfonating said alkylate fraction, and (E) recovering a mixture of organic sulfonates from the sulfonation mixture produced in (D).

The chlorination step (a) of the process of this invention is known in the art as underchlorination. In underchlorination the amount of chlorine and conditions of reaction are carefully controlled in order to partially chlorinate the alkanes to obtain a mixture comprising a minor portion of chloroalkanes, consisting essentially of monochloroalkanes, and a major portion of unreacted alkanes. In the process of this invention chlorination of up to about 25 mol percent of the-alkanes is preferred.

In carrying out the alkylation step (b) of the process of this invention conventional Friedel-Crafts catalysts, such as aluminum chloride, aluminum metal in admixture with aluminum cholride, aluminum bromide, zinc chloride, etc., is present in amounts of from about 0.1 to 4%, preferably from about 0.4 to 2% based on the weight of the chlorinated alkanes, and benzene is charged in a molar ratio of from about 2 to 12:1, preferably from about 4 to 6:1 of chlorinated alkanes present. The alkylation can be carried out under conventional benzene alkylation conditions, e.g., at temperatures of from about 20 to 100 C., preferably from about 30 to C. Reaction times in batch operations are about /2 to 1 hour after digestion of the reaction mixture, while in continuous operations a residence time of from about 2 to 15 minutes is generally adequate.

The desired hydrocarbon fraction can be recovered by allowing the alkylation mixture to stand until the heavy tarry layer has settled, decanting off the upper layer which can then be washed with aqueous base and then subjected to fractional distillation to remove unreacted benzene and alkanes, and a mixture of monoalkylbenzenes having up to about 35% by weight of 2-phenylalkanes, leaving the hydrocarbon fraction suitable for production of the organic sulfonates of this invention, which is then preferably subjected to further fractional distillation to obtain a mixture of hydrocarbons from which particularly useful organic sulfonates of this invention can be produced.

As already indicated, the hydrocarbon mixtures of my invention contain a certain amount of monoalkylate, which remains in the residue, after distillation of the bulk of the alkylate. The remainder of the hydrocarbon mixture consists essentially of disubstituted tetrahydronaphthalenes and indanes as well as diphenyl alkanes and dialkylbenzenes. The disubstituted tetrahydronaphthalenes and indanes may be formed during the alkylation process by condensation of one benzene molecule with a dichloroalkyl molecule formed during preparation of the monochloroalkyl reactant. The occurrence of disubstituted tetrahydronaphthalenes and indanes in the hydrocarbon mixtures of my invention may be identified by aromatization, to produce disubstituted naphthalenes and indenes. The diphenyl alkane fraction of the residues of our invention is identified by the fact that on fractional distillation, a distallate fraction is obtained having a relatively high refractive index and aniline point due to the high aromatic to aliphatic content of such fractions. The presence of dialkylbenzenes in alkylation residues has been suggested in the prior art and may be further indicated by a transalkylation reaction in which benzene and a dialkylbenzene are reacted in the presence of aluminum chloride to produce additional monoalkylbenzene.

However, while alkylation residues employed in the prior art for the production of oil soluble detergents consisted mainly of dialkyl and polyalkylbenzenes, the compositions of my invention contain such diand polyalkyl benzenes in relatively small amounts. Such relatively small amounts of diand polyalkylbenzenes occur in the hydrocarbon mixtures of my invention due to the utilization, in the alkylation process, of a large benzene to alkyl halide ratio in order to avoid polyalkylation, as well as utilization of the well known underchlorination technique in the chlorination of the n-alkanes to produce essentially a mixture of n-alkylmonochlorides and unchanged n-alkanes. In the latter procdure, some polychlorination inevitably occurs but such anomalous reaction is held to a convenient minimum.

The sulfonation of the hydrocarbon mixtures of this invention can be conducted by any convenional sulfonation technique using well-known sulfonating agents, e.g. sulfuric acid. Salts of the resulting sulfonation products can be produced by treatment with bases such as ammonium hydroxide, alkali and alkaline earth metal hydroxides, aliphatic amines, alkanolamines and the like and mixtures thereof.

The organic sulfonates of this invention are surprisingly effective as detergents even in cold water, and low foaming, being particularly useful in the laundering of fabrics; compositions thereof comparing favorably with commercial low foaming detergents, as illustrated in the examples hereinafter presented. The term low-foaming as used herein is intended to imply that the surfactant composition, in use, does not generate copious foam, or if a copious foam is initially produced, it is quickly dissipated. Low-foaming and controlled sudsing are generally equivalent terms in this art.

The organic sulfonates of this invention are surprisingly high in biodegradability, i.e. readily decomposed by micro-organisms, as determined by standard tests, as illustrated in the examples hereinafter presented. The organic sulfonates of this invention were found to be at least 80% biodegradable whereas anionic alkylbenzene detergents of low biodegradability, known as the hard detergents, are shown by such tests to be only about 30 to 40% biodegradable.

Detergent compositions particularly useful in the laundering of fabrics, can be prepared comprising from about 5 to 50 weight percent, preferably from about 8 to about 30 weight percent of the organic sulfonates of my invention as the surface active ingredients and one or more other detergents, fillers, builders or additives. Typically sodium tripolyphosphate, and tetrasodium pyrophosphate, sodium sulfate, sodium silicate, sodium orthosilicate and the like may be added as fillers and/or builders. Built compositions comprising the organic sulfonates of my invention may also contain other additives, such as carboxymethyl cellulose to prevent soil redeposition. Other additives may include optical brighteners, bleaches, colorants, desiccants to avoid balling of the composition particles and such other agents as the particular application for which the formulation is intended may require.

In addition to being valuable in laundering applications, the sulfonates of this invention may be used in dry cleaning formulations, for example in the form of solutions in dry cleaning solvents such as perchloroethylene, Stoddard solvent and the like. Furthermore, the organic sulfonates of my invention can be used in emulsification applications, or in the manufacture of specialty detergents, for example such as used in electroplating baths and the like. Also the organic sulfonates of this invention can be used as foam depressants.

The following examples illustrate in detail the preparation of the compositions of this invention and properties thereof. The examples are merely illustrative, and this invention is not intended to be confined to any limitation contained therein.

All percents given are percent by weight unless specified otherwise.

EXAMPLE I A mixture of 750 parts of benzene and 10 parts AlCl was heated to about 45 to 50. To this mixture was added with agitation during one-half hour, 500 parts of chlorinated normal tridecane mixture containing about 25 mol percent of normal tridecyl chlorides. The resulting reaction mass was digested at 45-50 for one-half hour and then permitted to stand until the suspended tar settled out. After separation of the tarry material, 28 parts, the remaining mass was washed with 5% aqueous caustic soda and then fractionally distilled to remove as distillate unreacted benzene and tridecane leaving the alkylation products. The alkylation products were further fractionally distilled at up to about 165 C. at 5 mm. Hg to remove as distillate a fraction consisting essentially of mono-tridecylbenzenes having about 2-phenyltridecane, leaving a hydrocarbon mixture composed of about 30% of monoalkylbenzenes of which about 90% were Z-phenylalkanes, about 11% of a mixture of dialkyltetrahydronaphthalenes and dialkylindanes and about 59% of a mixture of dialkylbenzenes and diphenylalkanes.

Six hundred parts of the hydrocarbon mixture was agitated with 110 parts of 100% sulfuric acid for one half hour at about 35 to 40 C., the spent acid layer was withdrawn and the acid washed product was contacted with about 24 parts Filtrol. The Washed product was sulfonated by heating for one hour at about 55 to 58 C. with about 930 parts 100% sulfuric acid after which A procedure as described in Example I was followed except that in place of the chlorinated normal tridecane mixture, chlorinated normal dodecane mixture containing about 25 mol percent normal dodecyl monochlorides was used, and a distillate fraction containing about 22% Z-phenyldodecane was collected, leaving a homologous hydrocarbon mixture of essentially the same composition as in Example I. A drum dried product was obtained and designated I-12.

EXAMPLE III A procedure as described in Example I was followed except that in place of the chlorinated normal tridecane mixture, a chlorinated normal tetradecane mixture containing about 25 mol percent normal tetradecyl monochlorides was used, and a distillate fraction containing about 8% 2-phenyltetradecane was collected, leaving a homologous hydrocarbon mixture of essentially the same composition as in Example I. A drum dried product was obtained and designated Il4.

EXAMPLE IV A hydrocarbon mixture was prepared by mixing 7.1 parts, 45.2 parts and 47.7 parts respectively of hydrocarbon mixtures obtained in the preparation of I-12, LB and I14, as described in Examples I to III. A drum dried product was obtained from the hydrocarbon mixture by following a procedure as described in Example I and the product designated I-blend.

EXAMPLE V A procedure similar to that described in Example I was followed except that the alkylation products were fractionally distilled up to about 177 C. at 0.5 mm. Hg, to remove as distillate essentially all monoalkylbenzenes, leaving a hydrocarbon mixture composed of about 3% of monoalkylbenzenes, of which about were 2-phenylalkanes, about 39% of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes, and about 58% of a mixture of dialkylbenzenes and diphenylalkanes.

The drum dried product obtained was designated II-13.

EXAMPLE VI Following a procedure as described in Example V, except that in place of the chlorinated normal tridecane, a mixture containing about 25 mol percent normal tetradecyl chlorides was used. A homologous hydrocarbon mixture of essentially the same composition was obtained.

A drum dried product was obtained and designated II-14.

EXAMPLE VII A hydrocarbon mixture was obtained by mixing 57 parts and 43 parts respectively of hydrocarbon mixtures obtained in the preparation of II-13 and II-14, as described in Examples V and VI.

A drum dried product was obtained by following a procedure as described in Example I and the product designated II-blend.

EXAMPLE VIII In order to illustrate the relative detersive and foaming properties of the organic sulfonates of this invention,

built compositions of each of the products described in the above examples were prepared and compared to commercial low foaming detergents in laundering towels as described in detail below.

The built compositions were prepared by mixing in a Hobart mixer parts of each of the drum dried products described in the above examples (having 9 parts of organic sulfonate and 1 part of sodium sulfate) with 44 parts of sodium sulfate and 36 parts of sodium tripolyphosphate as builders to obtain compositions having 10% of the respective organic sulfonate, 50% sodium sulfate and 40% sodium tripolyphosphate. The individual compositions are referred to in Tables I and II by the designation of the organic sulfonate component thereof.

A supply of randomly selected soiled Turkish hand towels was obtained from a commercial linen renting establishment.

Batches of 18 towels, weighing about 6 lbs. per batch, were laundered at a commercial coin-operated washing machine establishment using both RCA Whirlpool toploading and front-loading washing machines.

150 grams of built composition was added to each machine, in compliance with the machine manufacturers recommendation of grams of surface active agent per batch. Commercial detergents were used in the amounts recommended by the manufacturer thereof.

The temperature of the water added to the washing machines was 135145 F., the water having a hardness of 144 p.p.m. (as measured by the ASTM 11977-DI method).

Foam measurements were taken at three-minute intervals over a period of 9 consecutive minutes during the operation of the machines. In the top-loading machines the height of the foam was measured in inches. In the front-loading machines the height of the foam was measured as the fraction of the window height reached, i.e. it half of the window height was reached a rating of 50% was recorded; hence, a rating of 25% indicated that the foam reached about one quarter the height of the window and so on. The measurements at three-minute intervals were recorded; and a rating was assigned which denotes maximum foam height.

Each batch of towels was run through the normal operating cycle of the machine, then bundled and labeled and sent to a commercial laundry where they were dried and ironed.

The percentage reflectance of the finished towels was then determined by use of a Hunter Reflectometer using a green filter, with reflectance of pure magnesium oxide representing a 100% reflectance as standard. Average reflectance of each batch is represented in Table I and II as percentage based on the standard. With each detergent composition two laundering runs were carried out in toploading machines and one in side-loading machines.

TABLE I.TOP-LOADING WASHING MACHINE CODE.Foam rating: 0 to 1.5:Low foaming; 1.5 to 3: Moderate foaming; 3 to 4: High foaming. ADzA low sudsing allpurpose nonionic household detergent; aJAXzAlkylaryl sullonate anionic detergent; ALL:a controlled sudsing nonionie laundry detergent; DASl-IzA built all purpose low sndsing anionic detergent (from McCutcheon Detergent and Emulsiiier 1965 Annal).

TABLE II.FRONT-LOADING WASHING MACHINE Foaming (percent Door CODE.-Foam rating: 0 to 33=Low foaming; 33 to 50: Moderate foaming; Over 50: High foaming.

EXAMPLE IX In order to illustrate the low foaming properties of the organic sulfonates of this invention, dish washing tests were carried out according to the procedure described below.

An inverted conical container having a inch diameter spout attached to its narrow end is held at a height of 34 inches from the base of a 15 inch diameter and .5 inch deep wash basin. The container is filled with a solution of detergent preheated to 115 F. The spout of the container is opened and the solution is allowed to run into the wash basin to produce a foamy detergent solution. Each of forty 9 inch diameter glazed procelain plates in smeared on the top side with 0.5 gram of Crisco and the plates are stacked on top of each other. Five of the plates are immersed all at once in the detergent solution after which one plate is picked up and while still immersed in the solution is wiped five times with a dish cloth in a circular motion at the rate of one complete circular wiping per second. The operation is repeated on the bottom side of the plate for four times after which the plate is withdrawn from the solution. Additional plates are then washed until the last traces of foam disappear from the surface of the detergent solution. The number of plates washed prior to the disappearance of the foam is observed.

Built composition solutions were prepared from 2.5 grams of drum dried products of the above examples, 3.5 grams of sodium tripolyphosphate, 0.8 gram of sodium orthosilicate and 2.2 grams of sodium sulfate in 6 liters of distilled water. Solutions of equivalent concentrations of commercial high foaming detergents were also prepared.

Tests on the above-described solutions indicated that the compositions of this invention were low foaming, i.e. the last traces of foam disappeared after only one dish was washed, whereas ten to twenty dishes could be washed prior to the disappearance of the foam when solutions of commercial high foaming detergents were used.

EXAMPLE X A hydrocarbon mixture was obtained by mixing 12 parts, 48 parts and 40 parts, respectively, of hydrocarbon mixtures as obtained in the preparation of I12, I-13 and I-l4, as described in Examples I to III.

A portion of the hydrocarbon mixture was treated as described in Example I to obtain a drum dried product, designated A-I.

Another portion of the hydrocarbon mixture was fractionally distilled as described in Example V and the hydrocarbon mixture remaining after the distillation was treated as described in Example I to obtain a drum dried product, designated A-II.

Another portion of the hydrocarbon mixture was fractionally distilled to yield about distillate which was a hydrocarbon mixture composed of about 35% of monoalkylbenzenes, of which about were Z-phenylalkanes, about 14% of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes, and about 51% of a mixture of dialkylbenzenes and diphenylalkanes, which was then treated as described in Example I to obtain a drum dried product, designated A-III. A-III had a reflectance of over 65% (magnesium oxide standard), i.e. was a more intense white than the other drum dried products described above.

AI, A-II and A-III were tested for biodegradability by the Soap and Detergent Associations Semi-Continuous Activated Sludge Test. The tests indicated the average biodegradabilities of A-I, A-II and A-III to be 93.8%, 81.5% and over 90%, respectively.

EXAMPLE XI A built composition was prepared from the above-described product A-III, having 15% of organic sulfonate, 40% sodium tripolyphosphate, 28.5% sodium sulfate, 7% sodium ortho-silicate, 9% sodium chloride and 0.5% carboxymethylcellulose.

The built composition was tested in laundering fabrics in hot water, e.g. above 120 F., and cold water, e.g. 85- 90 F., of varying hardnesses, e.g. up to 300 p.p.m. and was found to have detergent and low foaming properties comparable to commercial low foaming detergents.

I claim:

1. An anionic surface active composition consisting essentially of sulfonates of a hydrocarbon mixture having (A) up to about 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of 2- phenylalkanes,

(B) from about 10% to 50% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and

(C) from about 35% to 90% by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

2. An anionic surface active composition as specified in claim 1, wherein the sulfonates are alkali metal, ammonium, or amine salts, said sulfonates being low foaming and highly biodegradable.

3. An anionic surface active composition as specified in claim 1 wherein the hydrocarbon mixture has (A) from about 15% to 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of 2- phenylalkanes,

(B) from about 10% to 40% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and

(C) from about 35 to 70% by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

4. An anionic surface active composition as specified in claim 3, wherein the sulfonates are alkali metal, ammonium, or amine salts, said sulfonates being low foaming and highly biodegradable.

5. An anionic surface active composition as specified in claim 4, wherein the sulfonates are sodium salts.

6. An anionic surface active composition as specified in claim 1, wherein the hydrocarbon mixture has (A) up to about 10% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said alkylbenzenes consisting predominantly of 2-phenylalkanes,

(B) from about 10% to 50% of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and

(C) from about 45% to by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

7. An anionic surface active composition as specified in claim 6, wherein the sulfonates are alkali metal, ammonium, or amine salts, said sulfonates being low foaming and highly biodegradable.

8. An anionic surface active composition as specified in claim 6, wherein the sulfonates are sodium salts.

Q. An anionic surface active composition as specified in claim 1, wherein the hydrocarbon mixture has (A) from about 30% to 40% by weight of monoalkyl- 'benzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said alkylbenzenes consisting predominantly of 2-phenylalkanes,

(B) from about 10% to15% by weight of a mixture of dialkylindanes and dialkyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and

(C) from about 45% to 60% by weight of a mixture of diphenylalkanes and dialkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms.

10. An anionic surface active composition as specified in claim 9, wherein the sulfonates are alkali metal, ammonium, or amine salts, said sulfonates being low foaming and highly biodegradable.

11. An anionic surface active composition as specified in claim 9, wherein the sulfonates are sodium salts.

12. As a new composition of matter a detergent composition consisting essentially of about 5 to 50% by weight of the product of claim 2 as a detergent component and the balance consisting of inorganic builders.

13. As a new composition of matter a detergent composition consisting essentially of about 5 to 50% by weight of an anionic surface active composition as specified in claim 2, wherein the sulfonates are sodium salts, and which additionally contains sodium tripolyphosphate, sodium sulfate and sodium orthosilicate as fillers and sodium carboxymethylcellulose to prevent soil redeposition.

14. A process for the preparation of an anionic surface active composition which comprises (A) passing chlorine in intimate contact with an essentially linear alkane hydrocarbon having 8 to 18 carbon atoms, or mixture thereof, in an amount insufiicient to chlorinate all the alkane and to produce primarily monochloroalkanes,

(B) reacting the chlorination mixture produced by step (A) with a large excess of benzene in the presence of a Friedel-Crafts catalyst under alkylating conditions to produce an alkylation mixture,

(C) recovering, as distilland, by fractional distillation of said alkylation mixture an alkylate fraction consisting essentially of (a) up to about 50% by weight of monoalkylbenzenes in which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms, said monoalkylbenzenes consisting predominantly of 2-phenylalkanes,

(b) from about 10% to 50% by weight of a mixture of dialkylindanes and dial-kyltetrahydronaphthalenes wherein the alkyl groups are essentially linear and contain from 1 to 14 carbon atoms, the sum of said alkyl carbon atoms being a maximum of 15 for each molecule, and

(c) from about 35% to 90% by weight of a mixture of diphenylalkanes and dialkylbenzenes in 1 1 which the alkyl groups are essentially linear and contain from 8 to 18 carbon atoms,

(D) sulfonating said alkylate fraction, neutralizing the sulfonate product and (E) recovering a mixture of alkylaryl sulfonates from the sulfonation mixture produced in (D).

15. A process for the preparation of an anionic surface active composition as specified in claim 14 wherein the sulfonation reaction mixture produced in (D) is neutralized with a compound of an'alkali metal compound, an alkaline earth metal compound, an ammonium compound or an organic amine.

16. A process for the preparation of an anionic surface active composition as specified in claim 14 wherein the alkylaryl sulfonates from the sulfonation mixture produced in (D) are recovered as sodium salts.

17. The process of claim 14 wherein up to about 25 mol percent of the alkanes are chlorinated.

12 18. The process of claim 14 wherein the mol ratio of benzene to chlorination mixture is in the range 4:1 to 6:1.

References Cited UNITED STATES PATENTS 10/ 1965 Swenson et al.

9/1966 Kapur. 10/ 1966 Kapur. 4/ 1967 J ones. 4/ 1967 Feighner et al. 260505 P. E. WILLIS, Assistant Examiner US. Cl. X.R. 

